title: Accurate analytic potential and Born-Oppenheimer breakdown functions for MgH and MgD from a direct-potential-fit data analysis.
abstract: New high-resolution visible Fourier transform emission spectra of the A (2)Π → X (2)Σ(+) and B' (2)Σ(+) → X (2)Σ(+) systems of (24)MgD and of the B' (2)Σ(+) → X (2)Σ(+) systems of (25,26)MgD and (25,26)MgH have been combined with earlier results for (24)MgH in a multi-isotopologue direct-potential-fit analysis to yield improved analytic potential energy and Born-Oppenheimer breakdown functions for the ground X (2)Σ(+) state of MgH. Vibrational levels of the ground state of (24)MgD were observed up to v" = 15, which is bound by only 30.6 ± 0.10 cm(-1). Including deuteride and minor magnesium isotopologue data allowed us also to determine the adiabatic Born-Oppenheimer breakdown effects in this molecule. The fitting procedure used the recently developed Morse/Long-Range (MLR) potential energy function, whose asymptotic behavior incorporates the correct inverse-power form. A spin-splitting radial correction function to take account of the (2)Σ spin-rotation interaction was also determined. Our refined value for the ground-state dissociation energy of the dominant isotopologue ((24)MgH) is D(e) = 11,104.25 ± 0.8 cm (-1), in which the uncertainty also accounts for the model dependence of the fitted D(e) values for a range of physically acceptable fits. We were also able to determine the marked difference in the well depths of (24)MgH and (24)MgD (with the deuteride potential curve being 7.58 ± 0.30 cm(-1) deeper than that of the hydride) as well as smaller well-depth differences for the minor (25,26)Mg isotopologues. This analytic potential function also predicts that the highest bound level of (24)MgD is v" = 16 and that it is bound by only 2.73 ± 0.10 cm(-1).
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, Ontario N2L 3G1, Canada.
authors.forename: Robert D E
authors.initials: RD
authors.lastname: Henderson
authors.forename: Alireza
authors.initials: A
authors.lastname: Shayesteh
authors.forename: Jason
authors.initials: J
authors.lastname: Tao
authors.forename: Carl C
authors.initials: CC
authors.lastname: Haugen
authors.forename: Peter F
authors.initials: PF
authors.lastname: Bernath
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Le Roy